EP0378067A2 - Positively working radiation-sensitive mixture containing a multifunctional alpha-diazo-beta-keto ester, process for its preparation and a radiation-sensitive recording material containing this mixture - Google Patents

Abstract

A description is given of a positively working radiation-sensitive mixture essentially containing a photoactive component and a water-insoluble binder which is soluble or at least swellable in aqueous alkaline solution, characterised in that the photoactive component is a multifunctional alpha -diazo- beta -ketoester of the general formula I …<IMAGE>… where… R<1> is an aliphatic cycloaliphatic or araliphatic or aromatic radical containing 4 to 20 carbon atoms in which individual CH2 groups may be replaced by oxygen or sulphur atoms or by …<IMAGE>… or NH groups and/or contain keto groups,… X is an aliphatic, cycloaliphatic, carbocyclic, heterocyclic or araliphatic radical containing 2 to 22 carbon atoms, in which individual CH2 groups may be replaced by oxygen or sulphur atoms or by the groups -NR<2>-, -C(O)-O-, -C(O)-NR<2>-, …<IMAGE>…, -NR<2>-C(O)-NR<3>-, -O-C(O)-NR<2>-, …<IMAGE>…, -O-C(O)-O- or CH groups may be replaced by …<IMAGE>…, where R<2> and R<3> are, independently of each other, hydrogen or an aliphatic, carbocyclic or araliphatic radical,… m is an integer from 2 to 10 and… n is an integer from 0 to 2,… with the proviso that m-n >/= 2. …<??>The radiation-sensitive mixture is particularly suitable for exposure with radiation having a wavelength of 190 to 300 nm.

Description

The invention relates to a positive-working radiation-sensitive mixture containing a photoactive component and a water-insoluble binder which is soluble in aqueous alkaline solution, but at least swellable.

Radiation-sensitive mixtures containing photoactive diazo derivatives and suitable for irradiation with high-energy UV radiation have been described in the literature for some time.

US Pat. No. 4,339,522 mentions positive-working radiation-sensitive mixtures which contain a diazo derivative of Meldrum's acid as the photoactive compound. This compound should be suitable for exposure to high-energy UV radiation in the range between 200 to 300 nm. However, it was found that when these mixtures are used, the photoactive compound is exudated at the higher processing temperatures frequently used in practice; the radiation-sensitive mixture loses its original activity, so that reproducible structuring is not possible.

In EP-A-0 198 674 and 0 262 864, in US-A-4,622,283 and in SU-A-1,004,359 2-diazo-cyclohexane-1,3-dione or -cyclopentane-1,3 -dione derivatives provided as photoactive compounds for radiation-sensitive mixtures of the type described. These compounds have a lower volatility but, depending on the substitution pattern present, show poor compatibility in the radiation-sensitive mixture. This is particularly evident when the layers dry by crystallizing the photoactive compound, by its insolubility in practical solvents or by a layer inhomogeneity caused by phase separation.

Further photoactive compounds which are sensitive and positive in the deep UV range are known from EP-A-0 129,694 and US-A-4,735,885. The compounds described in these documents have the disadvantage that the carbenes formed from them on exposure do not have sufficient stability in the matrix for the desired carboxylic acid formation. This leads to an insufficient solubility difference between the exposed and unexposed areas in the developer and thus to an undesirably high removal rate of the unexposed areas. A possible explanation for this phenomenon is given by C.G. Willson et al. in SPIE Vol. 771, "Advances in Resist Technology and Processing IV", 2 (1987).

EP-A-0 195 986 therefore proposes a-phosphoryl-substituted diazocarbonyl compounds as photoactive compounds since these have increased carbene stability. In practice, however, such compounds should only be used to a lesser extent, since atoms which can potentially be used as dopants, such as, for example, the phosphorus contained in these compounds, have to be meticulously excluded in the processing processes.

H. Sugiyama, E. Ebata, A. Mizushima and K. Nate present in their essay "Positive Excimer Laser Resist Prepared with Aliphatic Diazoketones" (SPIE Proc., 920, 51 (1988)) new a-diazoacetoacetates, which are used as photoactive Compounds in positive-working radiation-sensitive mixtures, in particular when using radiation in the deep UV range, are used. Since these are derivatives of acetoacetic acid, the keto group in the ß-position to the ester group is directly adjacent to a terminal methyl group. Radiation-sensitive mixtures which have the compounds mentioned as photoactive components show good bleaching properties, but their properties with regard to image differentiation are poor.

The object of the invention was therefore to provide a positive working radiation-sensitive mixture containing a photoactive compound with high sensitivity in the deep UV range, which does not have the numerous disadvantages described, and allows a good differentiation between the exposed and unexposed layer areas. In addition, the photoactive compounds contained in the radiation-sensitive mixture should be well tolerated with a wide variety of polymers which can be used in practice, in particular the binders, should not exude from the radiation-sensitive mixture and should have high thermal stability and practical sensitivity to light.

worin

• R' einen aliphatischen, cycloaliphatischen oder araliphatischen oder aromatischen Rest mit 4 bis 20 Kohlenstoffatomen, wobei einzelne CH₂-Gruppen durch Sauerstoff- oder Schwefelatome oder durch N -oder NH-Gruppen ersetzt sein können und/oder Ketogruppen enthalten,
• X einen aliphatischen, cycloaliphatischen, carbocyclischen, heterocyclischen oder araliphatischen Rest mit 2 bis 22 Kohlenstoffatome, wobei einzelne CH₂-Gruppen durch Sauerstoff- oder Schwefelatome oder durch die Gruppen -NR^2-, -C(O)-O-, -C(0)-NR^2-, -C(O)- N -, -NR^2-C(0)-NR^3-, -0-C(0)-NR^2-, -O-C(O)- N -, -O-C(O)-O- oder CH-Gruppen durch - N -ersetzt sein können, worin R² und R³ voneinander unabhängig für Wasserstoff oder einen aliphatischen, carbocyclischen oder araliphatischen Rest stehen,
• m eine ganze Zahl von 2 bis 10 und
• n eine ganze Zahl von 0 bis 2
• bedeuten, mit der Maßgabe, daß
• m-n ≧ 2 ist.

The object is achieved by providing a positive-working radiation-sensitive mixture comprising essentially a photoactive component and a binder which is insoluble in water but soluble in aqueous alkaline solution, but at least swellable, characterized in that a multifunctional -diazo-ß is used as the photoactive component ketoester of the general formula I is used,

wherein

• R 'is an aliphatic, cycloaliphatic or araliphatic or aromatic radical having 4 to 20 carbon atoms, it being possible for individual CH ₂ groups to be replaced by oxygen or sulfur atoms or by N or NH groups and / or to contain keto groups,
• X is an aliphatic, cycloaliphatic, carbocyclic, heterocyclic or araliphatic radical having 2 to 22 carbon atoms, individual CH ₂ groups being represented by oxygen or sulfur atoms or by the groups -NR ^2- , -C (O) -O-, -C ( 0) -NR ^2- , -C (O) - N -, -NR ^2- C (0) -NR ^3- , -0-C (0) -NR ^2- , -OC (O) - N -, -OC (O) -O- or CH groups can be replaced by - N -, where R ² and R ³ independently of one another represent hydrogen or an aliphatic, carbocyclic or araliphatic radical,
• m is an integer from 2 to 10 and
• n is an integer from 0 to 2
• mean with the proviso that
• mn ≧ 2.

In the preferred embodiment, R ₂ and R _{3 are} hydrogen, (C ₁ -C ₃ ) alkyl, (C ₆ -C ₁₂ ) aryl or (C ₆ -C ₁₁ ) aralkyl, the radicals - in particular aryl or aralkyl - on the core can also be substituted by alkyl, alkoxy, halogen or amino. R ₂ and R _{3 are} particularly preferably hydrogen or (C ₁ -C ₃ ) alkyl, but in particular hydrogen.

The radicals for R 'and X can optionally be substituted, in particular by (C ₁ -C ₃ ) alkyl, (C ₁ -C ₃ ) alkoxy, halogen, amino or nitro. R ¹ and X, which are substituted are preferably (Ci-C ₃₎ alkyl or (C ₁ -C ₃₎ alkoxy. The unsubstituted derivatives are preferred in particular when R 'and X are an alkyl radical.

The aliphatic radicals R ¹ can be either straight-chain or branched. The number of chain links here is preferably 4 to 10, in particular 4 to 8. This includes the particularly preferred pure carbon chains as well as the substituted ones, in which CH ₂ groups are replaced by oxygen atoms or -NH groups and / or keto groups are included, including Ether, keto, ester, amido or imido groups fall, ie also esters of carbamic acid. In the pure aliphatic radicals R ', ether groups occur particularly preferably twice per radical R'. If the chains are pure, in particular straight-chain, carbon chains, a limitation of the carbon number is not mandatory; aliphatic radicals with up to 20 carbon atoms can be used. However, the t-butyl radical is particularly preferred.

If R 'is a cycloaliphatic radical, the number of ring members is preferably 4, 5, 6 or 12, in particular 4, 5 or 6. The unsubstituted variants are particularly preferred. The cyclobutyl, cyclopentyl and cyclohexyl radicals are examples. The cyclohexyl radical is particularly preferred.

If R 'is an araliphatic radical, the number of links in the aliphatic part is 2 to 11, in particular 2 to 5. If it is a pure carbon chain in the aliphatic part, the number of C atoms is preferably 1 or 2. CH ₂ groups replaced by oxygen atoms, these can occur as a bridge between the aromatic and aliphatic part of the radical R ', but also in the aliphatic part. In both cases, it is particularly preferred if the remaining total number of carbon atoms as chain links in the aliphatic part of this radical is 1 or 2, the ether oxygen atom in the case of 2 carbon atoms being arranged as chain links in such a way that it is from both CH ₂ groups is adjacent. These include the benzyl, phenoxymethylene and benzyloxymethylene radicals. If, in addition, further CH ₂ groups in the aliphatic part of the araliphatic radical R ^{1 are} replaced by heteroatoms and / or substitutions are carried out on them, the total number of chain links in the aliphatic part is 3 to 5. These include phenyl or benzyl radicals bonded via ester groups , but also the benzyl or phenyl esters of carbamic acid. The aliphatic part can also represent the imido group of an aromatic dicarboxylic acid. The aromatic part of such a residue consists in particular of 6 carbon atoms. If the aromatic part of the araliphatic radical is directly adjacent to the keto group, that is to say is incorporated as an arylene radical, then there are no restrictions on the number of C atoms present at least for the aliphatic part occurring therein.

The aromatic radicals R ¹ preferably have no heteroatoms such as oxygen in their ring ystem on. If R 'is an aromatic radical, it preferably contains 6 to 12 carbon atoms, in particular 6 carbon atoms, ie corresponds to a phenyl radical. Aromatic radicals R 'are not preferred.

Overall, particularly preferred radicals are R 't-butyl, n-hexyl, nonyl, octadecyl, 2,5-dioxahexyl, cyclopentyl, cyclohexyl, benzyl, phenoxymethyl and benzyloxymethyl. The t-butyl, phenoxymethyl and cyclohexyl radical is particularly preferred.

X represents an aliphatic or cycloaliphatic radical, which can be saturated as well as unsaturated, a carbocyclic, heterocyclic or araliphatic radical with 2 to 22 carbon atoms, in particular with 2 to 17 carbon atoms. In these radicals, at least one CH ₂ group can also be replaced by heteroatoms such as oxygen, sulfur or by groups such as -NR ^2- , -C (O) -O-, -C (CO) -NR ^2- , -C (O) - _N -, -NR ^2- (CO) -NR ^3- , -0-C (CO) -NR ^2- , -OC (O) -N- or -OC (CO) -O- or CH groups -N- be replaced. Particularly preferred for the aliphatic or araliphatic radicals are those variants in which a maximum of two CH ₂ groups have been replaced by one type of the above-mentioned groups. If CH ₂ groups are replaced by heteroatoms, the number of these can preferably be at most 5, in particular at most 3. It is particularly preferred if all of the CH ₂ groups to be replaced are replaced by heteroatoms of one type.

If it is an unsubstituted, saturated or unsaturated aliphatic radical X, in the preferred variant it contains a maximum of 6 carbon atoms. The unsaturated aliphatic radicals X include, in particular, those whose CH ₂ or CH groups have not been replaced by heteroatoms or the above-mentioned groups. In their particular embodiment, they contain a maximum of one CC multiple bond; the number of chain links in such a radical is particularly preferred 4. The radicals X mentioned can be either 2- or 3-membered, but is preferred if X is 2-membered.

If X CH ₂ groups are replaced by heteroatoms in the aliphatic radicals, these are preferably bound by alkylene radicals each having at least 2 CH ₂ groups. If sulfur is the hetero atom in the aliphatic radical X, this is particularly preferably only once per radical. It is surrounded in particular by alkyl radicals with a maximum of 3 CH ₂ groups each. If oxygen is used as a hetero atom in the aliphatic radical, this can occur more frequently per radical, in particular 2 to 4 times. In this case, the alkylene radicals in which two oxygen atoms are incorporated contain at least 3 CH ₂ groups.

If the number of carbon atoms in the unsubstituted aliphatic radical is greater than 3, this alkylene radical is present in particular as a branched isomer. The t-butyl or t-pentyl radical is particularly preferred.

• Sofern die t-Butyl oder t-Pentylreste dreibindig sind, ist m mindestens 3. m = 4 wird bevorzugt erreicht, indem ein zweibindiger t-Pentyl- oder t-Butylrest im Rest X zweimal vorliegt. m = 4 wird auch erreicht, indem ein zweibindiger Propylrest am Rest X zweimal vorkommt.
• m = 6 wird bevorzugt erreicht, indem zwei dreibindige Reste (t-Butyl oder t-Pentyl) oder drei zweibindige Propylreste im Rest X vorliegen. m = 8 wird z.B. erreicht durch die Kombination von 4 zweibindigen Resten oder von 2 dreibindingen Resten mit einem zweibindigen Rest.

In the X radical, a plurality of alkyl radicals, in particular the t-butyl or t-pentyl radical, can also be connected via groups which replace heteroatoms or CH ₂ groups and which are mentioned above. This is particularly preferred if these residues are more than double-bonded:

• If the t-butyl or t-pentyl radicals are trivalent, m is at least 3. m = 4 is preferably achieved by having a double-bonded t-pentyl or t-butyl radical in the radical X twice. m = 4 is also achieved by having a double-bonded propyl radical on the X radical twice.
• m = 6 is preferably achieved by having two three-bonded radicals (t-butyl or t-pentyl) or three double-bonded propyl radicals in the X radical. m = 8 is achieved, for example, by combining 4 double-bonded residues or 2 triple-bonded residues with one double-bonded residue.

The more than two-bonded radical X can also be achieved by containing more than two-bonded heteroatoms: If a CH group is replaced by - N - in the aliphatic radical X, m values of 2 to 3 can be achieved. If two CH groups are replaced by - _N -, m can reach a maximum of 4; if these are part of a cycloaliphatic ring, m is a maximum of 2.

In all cases in which CH groups are replaced by - y - in the X radical, there is preferably no substitution of a CH ₂ group by another hetero atom or by one of the groups described above. The number of CH ₂ groups between the nitrogen hetero atom and the radical bonded to the radical X according to the general formula I is at least 2; in particular, this is the number 2.

Pure cycloaliphatic residues, i.e. unsubstituted, as variants of the radical X are not preferred. The cyclohexyl radical is mentioned in particular as the cycloaliphatic radical. However, this can be substituted, in particular by hydroxyl and / or alkyl or alkylene, the binding (i.e. m) of which is preferably determined by the number of alkylene substituents on the cycloaliphatic radical. A cyclohexyl radical which contains four methylene groups as substituents, which at the same time ensures the binding of the -diazo-β-ketoester units of the general formula I (m = 4), is very particularly preferred. It is particularly preferred if this radical X also contains a hydroxyl group, in particular a secondary hydroxyl group, so that n = 1.

Most of the time, the cycloaliphatic radicals as a variant of the radical X are more Combination of a cycloaliphatic and a chain-shaped aliphatic part. In this case, the cycloaliphatic part is preferably not substituted in such a way that CHz groups from this part are replaced by heteroatoms or by groups from the series mentioned above.

An exception is a six-membered ring (heterocycle) consisting of three carboxamide units, in which the a-diazo-β-ketoester units of the general formula I are coupled to the amido nitrogen via ethylene groups. m is therefore 3 and n is 0.

In diesem Fall wird als cycloaliphatischer Teil bevorzugt ein Cyclohexylrest eingesetzt, der sowohl einbindig wie auch zweibindig sein kann, letzteres bevorzugt in 1,4-Position. In beiden Fällen erfolgt die Verknüpfung einer der freien Valenzen der Reste

mit der -Diazo-ß-ketoester-Einheit nach der allgemeinen Formel I über ein Alkylenrest mit mindestens 2 CH₂-Einheiten. Sofern es sich um einen

Rest handelt, ist als verknüpfende Gruppe bevorzugt ein t-Butylenrest formuliert. Sofern es sich um einen

Rest handelt, d.h. die diskutierte Verknüpfung über das Sauerstoff atom dieser Gruppe erfolgt, wird bevorzugt ein Ethylenrest als verknüpfende Gruppe eingesetzt.However, if X is a combination of a pure cycloaliphatic part and one or more chain-shaped aliphatic parts with 2 or more carbon atoms, the cycloaliphatic part is in particular directly adjacent to a CH ₂ group which is replaced by one of the hetero atoms or groups mentioned above. The variant in which the cycloaliphatic part is directly adjacent to a nitrogen atom, in particular to the groups, is particularly preferred

In this case, a cyclohexyl radical is preferably used as the cycloaliphatic part, which can be both monovalent and double-bonded, the latter preferably in the 1,4-position. In both cases, one of the free valences of the residues is linked

with the -diazo-ß-ketoester unit according to general formula I via an alkylene radical having at least 2 CH ₂ units. Unless it's a

Radical, a t-butylene radical is preferably formulated as a linking group. Unless it's a

The remainder acts, ie the discussed linkage takes place via the oxygen atom of this group, an ethylene residue is preferably used as the linking group.

gebunden vorliegt. Das Stickstoffatom trägt in diesem Fall insbesondere einen Ethylenrest. Im Falle des Vorliegens eines araliphatischen Restes X ist der über das Stickstoffatom eines eine CH₂-Gruppe ersetzenden Restes

gebundene aliphatische Teil des Restes X insbesondere ein t-Butylen- oder ein Ethylenrest; ist der aliphatische Teil über das Sauerstoffatom gebunden, so ist dieser besonders bevorzugt ein Ethylenrest.If it is an araliphatic radical as a variant of group X, the aromatic part, in particular a phenyl radical, or if there is a double bond, a phenylene radical can be bound both via a nitrogen atom and via an oxygen atom. However, the nitrogen atom is preferred here too - if both atoms are available for selection. An example in which the aromatic part is bonded directly via an oxygen atom is an ether oxygen atom bonded to the a-diazo-β-ketoester unit via an ethylene group. The third variant in this case is the possibility that the aromatic radical, especially if it is monovalent, via the keto group of a radical

is bound. In this case, the nitrogen atom carries in particular an ethylene radical. If an araliphatic radical X is present, it is a radical which replaces a CH ₂ group via the nitrogen atom

bound aliphatic part of the radical X, in particular a t-butylene or an ethylene radical; if the aliphatic part is bonded via the oxygen atom, this is particularly preferably an ethylene radical.

The fact that an ethylene group is preferably bonded via the oxygen atom of the above-mentioned groups to replace a CH _z group in the X radical can also be transferred to aliphatic radicals, while both the ethylene radicals and higher aliphatic radicals, in particular from carbon chains, are also present via the nitrogen atom more than 3 carbon atoms. The t-butylene radical is preferred.

ersetzt. Der Rest

als Ersatz für ein CH-Gruppe liegt in der besonders bevorzugten Ausführungsform nur einmal in einem Rest X vor.If it is araliphatic and aliphatic radicals X, preferably a maximum of 2 CH ₂ groups by radicals such as

replaced. The rest

in the particularly preferred embodiment, a substitute for a CH group is present only once in a radical X.

In the variants of the radicals R ¹ and X shown above, m is preferably an integer from 2 to 8 and n is an integer from 0 to 2.

M is particularly preferably an integer from 2 to 6 and n = 0.

The a-diazo-.beta.-keto esters of the general formula I characterized in more detail above and used in the positive-working radiation-sensitive mixture according to the invention are outstandingly suitable as photoactive components. In particular, these compounds show a high absorption when exposed to radiation with a wavelength of 190 to 350 nm, preferably of 200 to 300 nm. The multifunctional ones Compounds according to general formula I and their preparation are described in German patent application P (Hoe 89 / K 002), which was filed at the same time.

In the process for the preparation of the -diazo-β-keto esters, it has proven to be particularly advantageous to first synthesize suitable precursors for β-keto esters of the general formula II and to do this in a subsequent reaction by means of a so-called diazo transfer into the -Diazo-β-keto esters of the formula I to transfer (see M. Regitz et al., Org. Prep. Proced., 1, 99 (1969)):

For this purpose, a β-keto ester of the general formula II (in which R and X have the meaning given in formula 1) is dissolved in 5 to 50 times, preferably 10 times the amount (based on the mixture) of a suitable solvent and the solution is dissolved a temperature between -15 ° C to + 15 ° C, preferably -5 ° C to + 5 ° C cooled. Suitable solvents are alcohols such as methanol, ethanol, alcohol ethers such as ethylene glycol monomethyl ether, chlorinated hydrocarbons such as dichloromethane or trichloromethane or preferably aliphatic nitriles such as acetonitrile or mixtures of these solvents. Those having a boiling point between 30 ° C. and 140 ° C. are particularly preferred. The actual implementation according to the invention can be carried out in 3 variants.

Option A:

The cooled solution is mixed with a 1 to 1.3-fold excess, based on the number of activated methylene groups to be reacted, of a diazo transfer reagent. Aromatic and aliphatic sulfonyl azides, such as toluenesulfonyl azide, 4-carboxyphenylsulfonyl azide, 2-naphthalenesulfonyl azide or methylsulfonyl azide, have proven particularly useful as transfer reagents. Based on the sulfonyl azide, the equimolar amount of a base, preferably a tertiary amine, is then added to the solution. The temperature of the mixture must be kept constant. Preferred amines are, for example, triethylamine, triisopropylamine or diazabicyclo [2.2.2] octane. The use of triethylamine as the base is particularly preferred. The mixture obtained is stirred for 5 to 50 minutes, preferably 10 to 15 minutes, at the predetermined temperature, warmed to room temperature and stirred for a further 1 to 24 hours, preferably 2 to 4 hours. Depending on the type of sulfonyl azide used, the sulfonylamide formed can precipitate out, so that it may be filtered off after the reaction has ended.

Variant B:

As an alternative to variant A, the β-keto ester of the general formula II and the amine can also be introduced under the conditions described above and the sulfonyl azide can then be metered in while maintaining the temperature.

Variant C:

However, a modified variant A has proven to be particularly favorable, in which the solution of the β-keto ester of the general formula II initially only with a 0.7 to 0.9-fold excess, based on the number of activated methylene groups to be reacted, of a sulfonyl azide , preferably toluenesulfonyl azide, is added and the total amount of the amine is added while maintaining the predetermined temperature. The mixture is then stirred, if necessary, while warming to room temperature. After about 10 to 120 minutes, the toluenesulfonyl azide can no longer be detected by chromatography. The mixture is then cooled again, if necessary, and this time the 0.6 to 0.1-fold excess of 4-carboxyphenylsulfonyl azide is added, so that a total excess of sulfonyl azide corresponding to Varinate A is formed. The raw products that are produced according to this variant show a high degree of purity.

The mixture obtained according to variants A to C is freed from the solvent and excess reagents and taken up in an inert, water-immiscible solvent, in particular dichloromethane or diethyl ether. To remove sulfonylamide residues, the mixture is washed twice with 5% potassium hydroxide solution and then with water until neutral, dried over a suitable drying agent and again freed from the solvent. The remaining residue, in particular when using variant C consisting almost entirely of pure a-diazo-β-keto ester of the general formula I, can be worked up by known methods, for example by means of crystallization or chromatography.

• 1. Entsprechend dem Schema 2 erfolgt eine Umsetzung eines monofunktionellen 5-Acyl-2,2-dialkyl-1,3-dioxan-4,6-dions (5-Acyl-meldrumsäure) der allgemeinen Formel III mit einem mehrwertigen Alkohol der allgemeinen Formel IV zum mehrfunktionellen ß-Ketoester der allgemeinen Formel II. Die Herstellung von 5-Acyl-meldrumsäure-derivaten der allgemeinen Formel III und deren Umsetzung zu ß-Ketoestern der allgemeinen Formel II ist für monofunktionelle Verbindungen bekannt und kann beispielsweise analog zu den Vorschriften von Y. Oikawa et al., J. Org. Chem., 43, 2087 (1987) durch Umsetzung von Säurechloriden mit Meldrumsäure, oder analog zu Vor schrift von P. Houghton und D.J. Lapham, Synthesis, 1982, 451ff, erfolgen. Die Produkte werden in ihrer Enolform isoliert.
  
• 2. Entsprechend dem Schema 3 erfolgt die Umsetzung eines monofunktionellen ß-Ketoesters, bevorzugt eines Methyl- oder Ethylesters der allgemeinen Formel V, mit einem mehrwertigen Alkohol der allgemeinen Formel IV zum mehrfunktionellen ß-Ketoester der allgemeinen Formel II. Die Umesterungsreaktion zur Herstellung von monofunktionellen ß-Ketoestern der allgemeinen Formel II ist bekannt und wird von A.R. Bader et al. in J. Amer. Chem. Soc., 73, 4195ff (1951) beschrieben.
  

The β-keto esters of the general formula II required for the conversion to the α-diazo-β-keto esters of the general formula I can be prepared in various ways known in the literature:

• 1. According to scheme 2, a monofunctional 5-acyl-2,2-dialkyl-1,3-dioxane-4,6-dione (5-acyl-meldrum's acid) of the general formula III is reacted with a polyhydric alcohol of the general formula IV for the multifunctional β-keto ester of the general formula II. The preparation of 5-acyl-meldrum's acid derivatives of the general formula III and their conversion to β-keto esters of the general formula II is known for monofunctional compounds and can be carried out, for example, analogously to the regulations of Y Oikawa et al., J. Org. Chem., 43, 2087 (1987) by reacting acid chlorides with Meldrum's acid, or analogously to the specification by P. Houghton and DJ Lapham, Synthesis, 1982, 451ff. The products are isolated in their enol form.
  
• 2. According to Scheme 3, the reaction of a monofunctional β-keto ester, preferably a methyl or ethyl ester of the general formula V, with a polyhydric alcohol of the general formula IV to give the multifunctional β-keto ester of the general formula II. The transesterification reaction to produce monofunctional β-keto esters of the general formula II are known and are described by AR Bader et al. in J. Amer. Chem. Soc., 73, 4195ff (1951).
  

In the reaction sequence according to Scheme 2, the relevant derivative of 5-acyl-meldrum's acid of the general formula III is mixed with the amount of the relevant mono- or polyfunctional alcohol of the general formula IV required for the desired degree of conversion, and the mixture is subsequently mixed in the 5- to 20 times, preferably 10 times the amount of a solvent which does not react with alcohols or Meldrum's acid, for example a ketone such as acetone or ethyl methyl ketone, or an ether such as 1,2-dimethoxyethane or dioxane, optionally with heating. The clear solution is heated to a temperature of 60 ° C. to 120 ° C., preferably to 80 ° C. to 100 ° C. The beginning of implementation is noticeable through lively development of carbon dioxide. The mixture is stirred for about 1 to 6 hours, preferably 2 to 3 hours, at the predetermined temperature until no more CO ₂ evolution can be observed.

The solvent is then removed in vacuo. Although the β-keto ester of general formula 11 in question is obtained in high purity, the product can optionally be further purified by methods known to those skilled in the art.

Particularly suitable derivatives of 5-acyl-meldrum's acid of the general formula III are those in which R 'is cyclobutyl, butyl, pentyl, cyclopentyl, hexyl, cyclohexyl, heptyl, octyl, nonyl or higher alkyl radicals having up to about 22 carbon atoms, which may by further alkyl radicals, alkoxyalkyl radicals, aryl radicals, alkoxyaryl radicals, aryloxyaryl radicals, halogen atoms or by other functional groups, for example by terminal acid ester functions, or in which individual CH ₂ groups are substituted by oxygen or sulfur atoms or by groups such as -C (O) -O -, -C (0) -NR ^2- , -NR ^2- C (0) -NR ^3- , -OC (O) -NR ^2- , -OC (O) -O-, -NR ^2- , wherein R ² and R ^{3 have} the meaning described above, can be replaced.

Particularly preferred radicals R 'are t-butyl, n-hexyl, 2,5-dioxahexyl, cyclopentyl, cyclohexyl, benzyl, phenoxymethyl and nonyl. The t-butyl, cyclohexyl and phenoxymethyl radical is particularly preferred.

Di-, tri- or higher-functional alcohols can be used as alcohols of the general formula IV; alcohols containing 2 to 6 OH groups per molecule are preferred. Difunctional alcohols of the general formula IV include, for example, ethylene glycol, propane-1,2-diol, propane-1,3-diol, 2,2-dimethyl-propane-1,3-diol, 3-chloropropane-1,2- diol, butane-1,2-diol, butane-1,3-diol, butane-2,3-diol, butane-1,4-diol, 2,3-dimethylbutane-2,3-diol, pentane 1,2-diol, pentane-1,5-diol, pentane-2,4-diol, 2-methyl-pentane-2,4-diol, hexane-1,6-diol, hexane-2,5-diol, 2,5-dimethyl-hexane-2,5-diol, 2-ethyl-hexane-1,3-diol, octane-1,8-diol, decane-1,10-diol, dodecane-1,2-diol, Dodecane-1,12-diol, phenylethylene glycol, or higher, optionally substituted and branched alkane diols, such as tartaric acid, dimethyl tartrate, diethyl tartrate, diisopropyl tartrate, 3-allyloxy-1,2-propane, dihydroxyacetone, tetraphenyl-1,2-ethanediol, in which may contain one or more methylene groups by oxygen atoms, such as in diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, 2,3-benzylidentrreit, radicals containing sulfur atoms, such as in 2,2-thiodiethanol, 1,8-dihydroxy-3,6-dithiaoctane, or radicals containing nitrogen atoms, for example in N-methyl -2,2'-iminodiethanol, N-butyl-2,2'-iminodiethanol, N-tert-butyl-2,2'-iminodiethanol, N-phenyl-2,2'-diiminodiethanol, or by the above designated groups can be substituted. In addition, unsaturated diols, such as, for example, 2-butene-1,4-diol, 2-butyne-1,4-diol, 3-hexyne-2,5-diol, 2,5-dimethyl-3-hexyne-2 , 5-diol, or cyclic diols, which in turn can be substituted by oxygen, sulfur or nitrogen atoms, such as cyclohexane-1,2-diol, cyclohexane-1,4-diol, 1,4-bis (hydroxymethyl) cyclohexane or 1,4-bis (2-hydroxyethyl) piperazine can be used with advantage. Such diols are generally commercially available. Further diols can be prepared, for example by reacting diols containing primary amino groups, for example 2-amino-2-methyl-1,3-propanediol, with monofunctional acid derivatives, such as carboxylic acid or sulfonic acid chlorides, or monofunctional isocyanates, but also with difunctional acid derivatives or corresponding isocyanates.

Trifunctional alcohols are preferably derived from glycerol, from higher α, β, ω-triols or from triethanolamine, with higher-chain derivatives, in particular ethoxylated compounds and heterocyclic compounds, such as e.g. 1,3,5-tris (2-hydroxyethyl) cyanuric acid can be used equally. Glycerol, 2-hydroxymethyl-2-methyl-propane-1,3-diol, 2-ethyl-2-hydroxymethyl-propane-1,3-diol, 2,3-isopropylidene erythruronic acid, hexane-1,2 are mentioned 6-triol, 1,1,1-triethanolamine, 1,1,1-tripropanolamine, as well as partially acetalized or ketalized sugar derivatives.

In addition, reaction products of tetrafunctional alcohols or aminotriols with acid derivatives, isocyanates or cyclic carbonates can also be used. Higher-quality alcohols of the general formula III are derived, for example, from condensation products of glycerol, pentaerythritol or from reaction products of difunctional acid derivatives or isocyanates with higher-quality alcohols or amino alcohols. The list of alcohols that can be used is by no means exhaustive; practically all alcohols can be used which have no further group reacting with acid esters or which clearly react with the formation of esters under the reaction conditions described.

In the production of β-keto esters of the general formula II by transesterification according to Scheme 3, monofunctional β-keto esters of the general formula V with alcohols of the general formula IV are used in such a way that a 5 to 200% excess, preferably a 10 to 50 % excess of a β-keto ester esterified with a low molecular weight alcohol, for example a methyl or ethyl ester, is reacted at 100 to 160 ° C., preferably at 120 to 140 ° C. To increase the solubility of the alcohol of the general formula IV in the β-keto ester of the general formula V, a solubilizer, such as dimethylformamide or N-methylpyrrolidone, can optionally be added. By applying a weak vacuum of 800 to 20 torr, preferably 400 to 100 torr, the equilibrium is distilled off formed lower alcohol continuously shifted in the desired direction. After the theoretical amount of lower alcohol has been distilled off, the excess low-esterified β-keto ester of the general formula V and, if appropriate, the added solubilizer are distilled off under high vacuum. The ß-keto ester of the general formula 11, which is often oily, remains in the residue in mostly very high purity, so that it can be used for the diazo transfer without further purification.

The low-esterified β-keto esters of the general formula V required in this reaction sequence are partly. commercially available or can be produced by numerous methods known from the literature. It is particularly preferred to prepare them from the corresponding derivatives of 5-acyl-meldrum's acid according to general formula 111. Although an additional reaction step compared to process variant 1 is followed, this variant can be used to improve yields and / or purer β-keto esters of the general Get Formula II.

The radiation-sensitive mixture according to the invention can contain one or more α-diazo-β-keto esters of the general formula I, in particular in the same proportion. However, it is preferred if only one photoactive compound is contained in the mixture. The concentration of the a-diazo-β-keto esters of the general formula I in the radiation-sensitive mixture according to the invention can vary within wide limits. In general, however, its concentration is in the range from 4 to 40% by weight, in particular from 6 to 30% by weight, based on the non-volatile constituents of the radiation-sensitive mixture.

The radiation-sensitive mixture according to the invention further contains at least one polymeric binder which is insoluble in water but soluble in aqueous alkaline solutions or at least swellable. The binder is distinguished in particular by the fact that it dissolves the constituents of the radiation-sensitive mixture according to the invention well and, in particular in the wavelength range from 190 to 300 nm, the lowest possible self-absorption, i.e. has a high transparency. In particular, this does not include those binders based on novolak condensation resins that have generally been used in combination with naphthoquinonediazides as photoactive components. Novolak condensation resins, even in combination with the above -diazo-β-keto esters, show a reduction in solubility compared to aqueous alkaline developers after imagewise exposure in the unexposed areas, but their self-absorption in the wavelength range desired for the exposure is undesirable high.

The novolak condensation resins mentioned can, however, be used in a mixture with other resins which are suitable as binders and have a higher degree of transparency. The mixing ratios mainly depend on the type of binder to be mixed with the novolak resin. In particular, its degree of self-absorption in the wavelength range mentioned, but also the miscibility with the other constituents of the radiation-sensitive mixture, play a decisive role. In general, however, the binder of the radiation-sensitive mixture according to the invention can contain up to 30% by weight, in particular up to 20% by weight, of a novolak condensation resin.

Suitable as binders are homo- or copolymers of p-hydroxystyrene and its alkyl derivatives, e.g. of 3-methylhydroxystyrene, as well as homo- or copolymers of other polyvinylphenols, e.g. of 3-hydroxystyrene or the esters or amides of acrylic acid with aromatics containing phenolic groups. Polymerizable compounds such as styrene, methacrylic acid methacrylate, acrylic acid methacrylate or the like can be used as comonomers in the copolymer.

Mixtures with increased plasma resistance are obtained when, for the production of copolymers of the above type, silicon-containing vinyl monomers, e.g. Vinyltrimethylsilane can be used. The transparency of these binders is generally higher in the area of interest, so that improved structuring is possible.

Homo- or copolymers of maleimide can also be used with the same success. These binders also show high transparency in the wavelength range described. Styrene, substituted styrenes, vinyl ethers, vinyl esters, vinylsilyl compounds or (meth) acrylic acid esters are also preferably used as comonomers here.

Finally, copolymers of styrene with comonomers can also be used, which bring about an increase in solubility in aqueous alkaline solutions. These include, for example, maleic anhydride, maleic acid semiesters or the like.

The binders mentioned can occur in mixtures, provided that they are miscible and do not impair the optical qualities of the radiation-sensitive mixture. However, preferred are binders containing a type of the above types.

The radiation-sensitive mixture according to the invention contains 60 to 96% by weight, in particular 70 to 94% by weight, of a binder, based on the proportion of the non-volatile constituents of the radiation-sensitive mixture.

Furthermore, dyes, pigments, wetting agents, adhesion promoters and leveling agents can be added to the radiation-sensitive mixture according to the invention to improve special requirements such as flexibility, adhesion and gloss.

The light-sensitive mixture according to the invention is preferably used in solvents such as ethylene glycol, glycol ethers such as glycol monomethyl ether, glycol dimethyl ether, glycol monoethyl ether or propylene glycol monoalkyl ethers, in particular propylene glycol methyl ether; aliphatic esters such as ethyl acetate, hydroxyethyl acetate, alkoxyethyl acetate, y-butyl acetate, propylene glycol monoalkyl ether acetate, in particular propylene glycol methyl ether acetate or amyl acetate; Ethers such as dioxane, ketones such as methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone and cyclohexanone; Dimethylformamide, dimethylacetamide, hexamethylphosphoric acid amide, N-methylpyrrolidone, butyrolactone, tetrahydrofuran, and dissolved in mixtures thereof. Glycol ethers, aliphatic esters and ketones are particularly preferred. In addition, solvent mixtures can be used, which include also contain aromatic hydrocarbons or xylene. Ultimately, the choice of solvent depends on the coating process used, the desired layer thickness and the drying conditions. The solvents must also be chemically neutral, i.e. they must not react irreversibly with the other layer components.

The solutions formed with the other constituents of the radiation-sensitive mixture generally have a solids content of 5 to 60% by weight, preferably up to 50% by weight.

According to the invention, a radiation-sensitive recording material is also claimed, consisting essentially of a substrate and the radiation-sensitive mixture applied thereon.

Suitable substrates are all materials from which capacitors, semiconductors, multilayer printed circuits or integrated circuits can be made or manufactured. In particular, surfaces made of pure silicon layers and thermally oxidized and / or aluminum-coated silicon material are to be mentioned, which can optionally also be doped, including all other substrates customary in semiconductor technology, such as silicon nitride, gallium arsenide, indium phosphide. Also suitable are the substrates known from the production of liquid crystal displays, such as glass, indium tin oxide; also metal plates and foils, for example made of aluminum, copper, zinc; Bimetallic and tri-metal foils, but also electrically non-conductive foils that are vapor-coated with metals, optionally with aluminum-coated Si0 ₂ materials and paper. These substrates can be subjected to a temperature pretreatment, surface roughened, etched or to achieve desired properties, such as. B. increase in hydrophilicity, be treated with chemicals.

In a particular embodiment, the radiation-sensitive mixture can contain an adhesion promoter for better adhesion in the resist or between the resist and the substrate. In the case of silicon or silicon dioxide substrates, adhesion promoters of the aminosilane type are used, e.g. 3-aminopropyltriethoxysilane or hexamethyl-disilazane in question.

Examples of supports which can be used for the production of photomechanical recording layers such as printing forms for letterpress printing, planographic printing, screen printing, gravure printing and relief copies are aluminum plates, optionally anodized, granular and / or silicated aluminum plates, zinc plates, steel plates, which may have been processed with chrome, as well as plastic films or paper.

The recording material according to the invention is exposed imagewise. Sources of actinic radiation are: metal halide lamps, carbon arc lamps, xenon lamps and mercury vapor lamps. Exposure to high-energy radiation such as laser, electron or X-ray radiation can also take place. However, lamps which can emit light of a wavelength of 190 to 260 nm are particularly preferred, i.e. in particular xenon and / or mercury vapor lamps. Laser light sources can also be used, e.g. Excimer lasers, in particular KrF or ArF lasers, which emit at 249 or 193 nm. The radiation sources must have sufficient emission in the wavelength ranges mentioned, but on the other hand must also be sufficiently transparent to actinic light in the range mentioned.

The invention further relates to a method for producing a radiation-sensitive recording material. The radiation-sensitive mixture can be applied to the substrate by spraying, rolling, knife coating, pouring, by flow coating, spin coating and dip coating or by means of slot dies. The solvent is then removed by evaporation, so that the radiation-sensitive layer remains on the surface of the substrate. The removal of the solvent can optionally be promoted by heating the layer to temperatures of up to 140 ° C. However, the mixture can also first be applied to the intermediate carrier in the above-mentioned manner, from which it is transferred to the final carrier material under pressure and elevated temperature.

The layer thickness varies depending on its area of application. It is between 0.1 and 100 μm, in particular between 0.3 and 10 μm.

The layer is then exposed imagewise. Actinic radiation is usually used. UV lamps which emit light with a wavelength of 190 to 300 nm are preferably used for the irradiation. An image pattern is then exposed in the radiation-sensitive layer by development, in which the layer is treated with a developing solution which dissolves or removes the irradiated areas of the material.

Solutions of reagents such as e.g. Silicates, metasilicates, hydroxides, hydrogen or dihydrogen phosphates, carbonates or hydrogen carbonates, of alkali and / or alkaline earth metal, in particular of ammonium ions, but also ammonia and the like are used. Metal ion-free developers are described in US-A-4,729,941, EP-A-0 062 733, US-A-4,628,023, US-A-4,141,733, EP-A-0 097 282 and EP-A-0 023 758. The content of these substances in the developer solution is generally 0.1 to 15% by weight, preferably 0.5 to 5% by weight, based on the weight of the developer solution. Metal ion-free developers are used in particular. If necessary, smaller amounts of a wetting agent can be added to the developers in order to facilitate the detachment of the exposed areas in the developer.

The developed resist structures are hardened if necessary. This is generally done by heating the resist structure on a hot plate to a temperature below the flow temperature and then exposing the entire area to UV light from a xenon mercury vapor lamp (range from 200 to 250 nm). As a result of this post-curing, the resist structures are crosslinked, so that the structures generally have a flow resistance up to temperatures of over 200 ° C. The post-curing can also be carried out without increasing the temperature by irradiation with UV light. This is especially true when high-energy radiation is used, e.g. Electron radiation.

The radiation-sensitive mixture according to the invention is preferably used in lithographic processes for the production of integrated circuits or of discrete electrical components. The recording material produced from the mixture serves as a mask for the following process steps. These include e.g. etching the substrate, implanting ions into the substrate or depositing metals or other materials on the substrate.

The mixtures according to the invention show a comparable high sensitivity to light under the usual conditions when exposed to light in the DUV range compared to the known materials (comparative example see below) when they are irradiated with light of a wavelength of 190 to 300 nm. As advantages, however, they show a higher thermal stability than the known materials and an excellent compatibility.

The following examples illustrate the preparation of the a-diazo-β-keto esters according to the general formula I.

Manufacturing examples: example 1 Preparation of a difunctional a-diazo-β-keto ester of the general formula I: bis-2,9-diazo-1,10-dicyclohexyl-4,7-dioxa-1,3,8,10-tetraoxo-decane (3) Step 1: 5- (1-cyclohexyl-1-hydroxy-methylidene) -2,2-dimethyl-1,3-dioxane-4,6-dione (1)

A solution consisting of 144.1 g (1.0 mol) of 2,2-dimethyl-1,3-dioxane-4,6-dione and 158.2 g (2.0 mol) of pyridine in 500 ml of dichloromethane is made up to 10 ° C cooled. At this temperature, 146.6 g (1.0 mol) of cyclohexane carboxylic acid chloride are added dropwise with stirring. The mixture is then warmed to room temperature and, after 4 hours, a mixture of 500 g of ice, 500 ml of water and 100 ml of concentrated hydrochloric acid is added. The organic phase is washed twice with 400 ml of water, dried over magnesium sulfate and then freed from the solvent.

An oily red residue remains, which is boiled twice with 600 ml each of n-hexane with the addition of activated carbon. When cooling, fine, pale yellow crystals of the n-hexane solution fall off desired connection (1). After a further recrystallization from n-hexane, white crystals of compound (1) with a melting point of 82 C. are obtained in a yield of 57%.

Level 2: 1,10-dicyclohexyl-4,7-dioxa-1,3,8,10-tetraoxo-decane (2)

12.4 g (0.2 mol) of ethylene glycol and 101.8 g (0.4 mol) of the compound (1) described above are introduced into 800 ml of ethyl methyl ketone and slowly warmed up. A strong carbon dioxide development begins at around 60 ° C. The solution is refluxed for 2.5 hours. After the reaction mixture has cooled, the solvent is removed in vacuo. An oily residue remains which consists practically exclusively of the desired difunctional β-keto ester (2). It is used as the starting product for the next stage without further purification.

Level 3: Bis-2,9-diazo-1,10-dicyclohexyl-4,7-dioxa-1,3.8,10-tetraoxo-decane (3)

IR (Film): 2.140,7 cm^-1 (C = N₂)11.5 g (30 mmol) of the β-keto ester (2) are dissolved in 130 ml of acetonitrile and cooled to 0 ° C. 9.85 g (50 mmol) of tosyl azide are added to the cooled solution and then 6.6 g (65 mmol) of triethylamine are added dropwise in such a way that the temperature does not rise above 5 ° C. The mixture is stirred at this temperature for 10 minutes; then it is warmed to room temperature. After two hours, the reaction mixture can no longer be detected by thin layer chromatography (silica gel, eluent: CH ₂ C1 ₂ ). 3.4 g (15 mmol) of 4-carboxyphenylsulfonyl azide are added to the mixture while cooling. After further reaction for a further 2 hours at room temperature, a precipitate forms. The mixture is concentrated on a rotary evaporator, taken up in diethyl ether, extracted twice with 5% strength aqueous potassium hydroxide solution and washed neutral with water. The organic phase is separated off and dried over magnesium sulfate. After concentrating them, 12.2 g of a slightly yellowish oil remain, which is freed from solvent residues by applying a high vacuum. Chromatography on silica gel with dichloromethane as the eluent gives the colorless product (3), which has the following composition.

IR (film): 2,140.7 cm ^-1 (C = N ₂ )

Example 2 Preparation of an unsaturated, difunctional a-diazo-ß-keto ester of the general formula I: bis-4,13-diazo-6,11-dioxa-2,2,15,15-tetramethyl-3,5,12,14-tetraoxo -hexadec-8-in (5) Step 1: 6,11-dioxa-2,2-15,15-tetramethyl-3,5,12,14-tetraoxohexa-dec-8-in (4)

8.6 g (0.1 mol) of 2-butyne-1,4-diol are heated to 120 ° C. with stirring together with 47.5 g (0.3 mol) of 4,4-dimethyl-3-oxovaleric acid methyl ester. The resulting methyl alcohol is converted into a the cooled template is distilled off. After about 4 hours, the theoretically calculated amount of methyl alcohol has distilled off. The homogeneous solution is heated to 140 ° C. for 1 hour and excess 4,4-dimethyl-3-oxovaleric acid is distilled off while applying a vacuum (10 torr). The remaining residue practically corresponds to the pure compound (4) and is processed without further purification.

Level 2: Bis-4,13-diazo-6,11-dioxa-2,2,15,15-tetramethyl-3,5,12,14-tetraoxo-hexadec-8-in (5)

IR (KBR): 2.137,9 cm-¹, 2.160,0 cm^-1 (Schulter) (C = N₂).30.4 g (90 mmol) of the product (4) described above are dissolved in 250 ml of acetonitrile and cooled to 0.degree. 33.6 g (170 mmol) of tosyl azide are added dropwise with stirring in such a way that the temperature does not exceed 5 ° C. The mixture is warmed to room temperature. After about 2 hours no more tosyl azide can be detected by thin layer chromatography. 4.5 g (20 mmol) of 4-carboxybenzenesulfonyl azide are added to the mixture. After two hours, the solvent is distilled off on a rotary evaporator, the solid residue is taken up in dichloromethane and washed with 2 × 200 ml of 4% potassium hydroxide solution and then with 200 ml of water. After drying and removal of the solvent, an oil remains, which begins to crystallize in the refrigerator. The crystal cake (29.8 g = 85% of theory) is recrystallized from n-hexane. 22.2 g of colorless crystals of compound (5) with a melting point of 69-70 ° C. are obtained.

IR (KBR): 2,137.9 cm- ¹ , 2,160.0 cm ^-1 (shoulder) (C = N ₂ ).

Example 3 Preparation of a trifunctional α-diazo-β-keto ester of the general formula I: Tris - [(5-diazo-3,8-dioxa-4,6-dioxo-8-phenyl) octyl] amine (8) Step 1: 5- (1-Hydroxy-2-phenoxyethylidene) -2,2-dimethyl-1,3-dioxane-4,6-dione (6)

In a solution of 72.1 g (0.5 mol) of 2,2-dimethyl-1,3-dioxane-4,6-dione and 79.1 (1.0 mol) of pyridine in 250 ml, cooled to 8 ° C. Dichloromethane is added dropwise 93.8 g (0.55 mol) of phenoxyacetic acid chloride in such a way that the temperature does not rise above 10 ° C. The mixture is stirred for 2.5 hours at room temperature, mixed with a mixture of 250 g of ice, 250 ml of water and 30 ml of concentrated hydrochloric acid and shaken out. The organic phase is washed twice with 100 ml of water each time and dried over magnesium sulfate. The solvent is distilled off, leaving a solid which is recrystallized from t-butyl methyl ether. 72 g (52% of theory) of white crystals of compound (6) are obtained, which melt at 85-87 ° C. with decomposition.

Level 2: Tris - [(3,8-dioxa-4,6-dioxo-8-phenyl) octyl] amine (7)

3.6 g (20 mmol) of triethanolamine and 18 g (64 mmol) of the compound (6) described above are heated to reflux in 140 ml of methyl ethyl ketone. After the evolution of carbon dioxide has ended, the mixture is heated under reflux for a further hour and then the solvent is distilled off. There remains highly viscous, reddish oil of compound (7) which is used for the subsequent reaction step without further purification.

Level 3: Tris - [(5-diazo-3,8-dioxa-4,6-dioxo-8-phenyl) octyl] amine (8)

IR (KBr): 2.142 cm^-1 (C = N₂)The total amount of oil (7) formed in stage 2 (about 20 mmol) is dissolved in 120 mol acetonitrile and cooled to 0 ° C. 6.5 g (65 mmol) of triethylamine are added to the cooled solution with stirring, and 12.8 g (65 mmol) of tosyl azide are then added dropwise in such a way that the temperature does not rise above 5 ° C. The mixture is stirred at this temperature for 10 minutes and then warmed to room temperature. After three hours, the clear solution is evaporated to dryness on a rotary evaporator, taken up in diethyl ether and extracted twice with 100 ml of 5% aqueous potassium hydroxide solution and then washed neutral with water. The organic phase is separated off and dried over magnesium sulfate. After concentrating on a rotary evaporator, 15.4 g of a slightly brownish oil remain, which is freed from solvent residues by applying a high vacuum. Crystals begin to separate. The crystal slurry is recrystallized from toluene, giving 12.1 g of colorless crystals of compound (8), which melt at 104 ° C. with the start of decomposition.

IR (KBr): 2.142 cm ^-1 (C = N ₂ )

Example 4 Preparation of a trifunctional a-diazo-β-keto ester of the general formula I: Tris - [(5-diazo-7,7-dimethyl-4,6-dioxo-3-oxa) octyl] amine (10) Step 1: Tris - [(7,7-dimethyl-4,6-dioxo-3-oxa) octyl] amine (9)

7.5 g (50 mmol) of triethanolamine and 30 g (189 mmol) of 4,4-dimethyl-3-oxovaleric acid methyl ester are heated at 130 ° C. for 5 hours with stirring. The methyl alcohol formed is distilled off. The excess monofunctional β-keto ester is then distilled off in vacuo. What remains is a light yellow oil, which proves to be an almost pure compound (9), so that it can be used for the subsequent reaction step without further purification.

Level 2: Tris - [(5-diazo-7,7-dimethyl-4,6-dioxo-3-oxa) octyl] amine (10)

IR (KBr): 2.171 cm-', 2.134 cm-¹ (Schulter) (C=N2)18 g (34 mmol) of compound (9) from stage 1 are dissolved in 180 ml of acetonitrile and cooled to 0 ° C. 11.4 g (112 mmol) of triethylamine are added to the cooled solution with stirring, and 22.4 g (112 mmol) of tosyl azide are then added dropwise in such a way that the temperature does not rise above 5 ° C. The mixture is stirred at this temperature for 10 minutes and then warmed to room temperature. After two hours, the clear solution is evaporated to dryness on a rotary evaporator, taken up in diethyl ether, extracted twice with 100 ml of 5% aqueous potassium hydroxide solution and washed neutral with water. The organic phase is separated off and dried over magnesium sulfate. After concentrating on a rotary evaporator, 18.4 g of a slightly brownish oil remain, which is freed from solvent residues by applying a high vacuum. Crystals begin to separate. The crystal slurry is recrystallized from cyclohexane, 15.4 g of colorless crystals of compound (10) being obtained, which melt at 101 ° C. with slow decomposition.

IR (KBr): 2.171 cm- ', 2.134 cm- ¹ (shoulder) (C = N2)

Example 5 Preparation of a trifunctional a-diazo-β-keto ester of the general formula I: N-phenyl-N '- [1,1-bis- (5-cyclohexyl-4-diazo-3,5-dioxo-2-oxapentyl) -6-cyclohexyl-5-diazo-4,6-dioxo-3-oxa-hexyl] urea (13) Step 1: N-phenyl-N '- [1,1-bis-hydroxymethyl-2-hydroxyethyl] urea (11)

66.6 g (0.55 mol) of tris (hydroxymethyl) aminomethane are dissolved in 200 ml of distilled water and 400 ml of acetone are added. While stirring, 59.6 g (0.5 mol) of phenyl isocyanate are added dropwise at 20 ° C., a heavy, white precipitate being formed. After the addition has ended, the mixture is stirred for a further 2 hours and the precipitate is filtered off with suction. It is then digested successively in 150 ml of water, acetone and diethyl ether. Finally, the compound (11) obtained in practically pure analysis is dried at 75 ° C.

Level 2: N-phenyl-N '- [1,1-bis- (5-cyclohexyl-3,5-dioxo-2-oxapentyl) -6-cyclohexyl-4,6-d ioxo-3-oxa-hexyl] - urinary (12)

8.4 g (35 mmol) of the compound (11) and 22.0 g (119 mmol) of 3-cyclohexyl-3-oxo-propionic acid methyl ester are heated in a Claisen apparatus to 130 ° C for 4 hours while applying a weak vacuum, during which time the methyl alcohol formed is distilled off. Then the excess 3-cyclohexyl-3-oxo-propionic acid methyl ester (bp. 75-76 ° C / 0.05 Torr) is distilled off from the mixture. A brownish, highly viscous oil of N-phenyl-N'-1,1-bis- (5-cyclohexyl-3,5-dioxo-2-oxapentyl) -6-cyclohexyl-4,6-dioxo-3 remains -oxa-hexyl-urea (12), which is used without further purification.

Level 3: N-phenyl-N- [1,1-bis- (5-cyciohexyl-4-diazo-3,5-dioxo-2-oxapent) -6-cyclohexyl-5-diazo-4,6-dioxo-3 - oxahexyl] urea (13)

IR (KBr): 2.141,2 cm-' (C=N2)13.72 g (20 mmol) of the compound (12) described above and 6.6 g (65 mmol) of triethylamine are dissolved in 140 ml of acetonitrile and cooled to 0 ° C. 12.8 g (65 mmol) of toluenesulfonyl azide are added dropwise to this solution in such a way that the temperature does not exceed 5 ° C. The mixture is warmed to room temperature and stirred for 4 hours. The clear solution is then evaporated to dryness on a rotary evaporator, the residue is taken up in dichloromethane, extracted twice with 100 ml of 5% strength aqueous potassium hydroxide solution and washed neutral with water. The organic phase is separated off and dried over magnesium sulfate. After concentrating on a rotary evaporator, 12.4 g of a slightly brownish oil remain, which is freed from solvent residues by applying a high vacuum. The oil is again taken up in a small amount of dichloromethane and eluted on a silica gel column. By using dichloromethane / ethyl acetate 5: 1 as the mobile phase, after concentrating the solvent, 8.5 g (55.6% of theory) of a slightly yellowish oil of compound (13) are obtained.

IR (KBr): 2.141.2 cm- '(C = N2)

Example 6 Preparation of a trifunctional a-diazo-β-keto ester of the general formula I: 2,2,2-tris- [4- (7-cyclohexyl-6-diazo-1,4-dioxa-5,7-dioxo-heptyl) - phenyl] ethane (15) Step 1: 2,2,2-tris [4- (7-cyclohexyl-1,4-dioxa-5,7-dioxoheptyl) phenyl] ethane (14)

8.77 g (20 mmol) of 2,2,2-tris [4- (2-hydroxy-ethoxy) phenyl] ethane (prepared by reacting tris (4-hydroxyphenyl) ethane with 2-chloroethanol) are heated with 18.4 g (100 mmol) of 3-cyclohexyl-3-oxopropionic acid methyl ester in a Claisen apparatus under a weak vacuum at 130 ° C. for 4 hours. The methyl alcohol formed is distilled off, as is the excess 3-cyclohexyl-3-oxopropionic acid methyl ester (bp. 75-76 ° C./0.05 Torr). A slightly brownish, highly viscous oil of compound (14) remains which can be used without further purification.

Level 2: 2,2,2-tris [4- (7-cyclohexyl-6-diazo-1,4-dioxa-5,7-dioxo-heptyl) phenyl] ethane (15)

IR (KBr): 2.141,2 cm^-1 (C=N₂)8.95 g (10 mmol) of the compound (14) described above and 3.5 g (35 mmol) of triethylamine are dissolved in 100 ml of acetonitrile and cooled to 0 ° C. 6.9 g (35 mmol) of toluenesulfonyl azide are added dropwise to this solution in such a way that the temperature does not exceed 5 ° C. The mixture is warmed to room temperature and stirred for 4 hours. The clear solution is then evaporated to dryness on a rotary evaporator, taken up in dichloromethane, extracted twice with 100 ml of 5% strength aqueous potassium hydroxide solution and washed neutral with water. The organic phase is separated off and dried over magnesium sulfate. After concentrating on a rotary evaporator, 9.4 g of a slightly brownish oil remain, which is freed from solvent residues by applying a high vacuum. The oil immediately begins to crystallize. The crystal slurry is recrystallized from t-butyl methyl ether. Compound (15) is obtained in the form of a white powder in virtually quantitative yield and has a melting point of 96 C.

IR (KBr): 2.141.2 cm ^-1 (C = N ₂ )

Example 7 Preparation of a tetrafunctional a-diazo-β-keto ester of the general formula I: N-1,1-bis- (5-cyclohexyl-4-diazo-3,5-dioxo-2-oxapentyl) -6-cyclohexyl-5 -diazo-4,6-dioxo-3-oxa-hexyl] -O- [6-cyclohexyl-5-diazo-4,6-dioxo-3-oxa-hexyl) urethane (18) Step 1: N- (bis-1,1-hydroxymethyl-2-hydroxyethyl) -O- (2-hydroxyethyl) urethane (16)

88.6 g (1 mol) of ethylene carbonate and 121.2 g of tris (hydroxymethyl) aminomethane are mixed together. The mixture heats up and is kept at a maximum of 70 ° C by external cooling. After the exothermic reaction has ended, the mixture is stirred at this temperature for a further 6 hours. When cooling, a melt forms, which is recrystallized from acetone. 198 g of white crystals are obtained, which melt at 112 ° C.

Level 2: N- [1,1-bis (5-cyclohexyl-3,5-dioxo-2-oxa-pentyl) -6-cyclohexyl-4,6-dioxo-3-oxa-hexyl] -0- [6-cyclohexyl -4,6-dioxo-3-oxa-hexyl) urethane (17)

6.27 g (30 mmol) of compound (16) from stage 1 are heated to 140 ° C. with 25.0 g (136 mmol) of methyl cyclohexylacetoacetate. The theoretical amount of methyl alcohol is distilled off from the mixture in the course of 4 hours. The excess of the cyclohexylacetoacetic acid methyl ester is then distilled off in vacuo, and the slightly brownish residue of compound (17) is processed without further purification.

Level 3: N- [1,1-bis (5-cyclohexyl-4-diazo-3,5-dioxo-2-oxapentyl) -6-cyclohexyl-5-diazo-4,6-dioxo-3-oxa-hexyl ] -O- [6-cylcohexyl-5-diazo-4,6-dioxo-3-oxa-hexyl) urethane (18)

IR (KBr): 2.140,6 cm^-1 (C=N2)24.5 g (30 mmol) of compound (17) are dissolved in 250 ml of acetonitrile and cooled to 0 C. 13.4 g (130 mmol) of triethylamine are added to the cooled solution with stirring. 25.6 g (130 mmol) of tosyl azide are then added dropwise in such a way that the temperature does not rise above 5 ° C. The mixture is stirred at this temperature for 10 minutes and then warmed to room temperature. After 3 hours, the clear, reddish-brown solution is evaporated to dryness on a rotary evaporator, the residue is taken up in dichloromethane, extracted twice with 100 ml of 5% aqueous potassium hydroxide solution and washed neutral with 5% aqueous sodium chloride solution. The organic phase is then separated off and dried over magnesium sulfate. After concentrating the solution on a rotary evaporator, 26.7 g of a brownish oil remain, which is freed from solvent residues by applying a high vacuum. By adding diethyl ether, small amounts of pale yellowish crystals begin to separate out. These are separated off and prove to be N- [1,1-bis (5-cyclohexyl-4-diazo-3,5-dioxo-2-oxapentyl) -6- cyclohexyl-5-diazo-4,6-dioxo-3-oxa-hexyl] -O- [6-cyclohexyl-5-diazo-4,6-dioxo-3-oxa-hexyl) urethane (18). The remaining solution is chromatographed on silica gel with dichloromethane to isolate residual traces of compound (18). Excess tosyl azide is eluted. The main fraction is eluted with a mixture of dichloromethane / ethyl acetate (75% of the amount used), the crystallization of compound (18) commencing after the solvents have been distilled off.

IR (KBr): 2,140.6 cm ^-1 (C = N2)

Example 8 Preparation of a tetrafunctional a-diazo-β-keto ester of the general formula 1: N, N, N ', N'-tetrakis [6-cyclohexyl-5-diazo-4,6-dioxo-3-oxa-hexyl] ethylenediamine (20) Step 1: N, N, N ', N'-tetrakis-6-cyclohexyl-4,6-dioxo-3-oxahexyl-ethylenediamine (19)

5.9 g (25 mmol) of N, N, N ', N'-tetrakis (2-hydroxyethyl) ethylenediamine are mixed with 33.1 g (180 mmol) of 3-cyclohexyl-3-oxo-propionic acid methyl ester for 7.5 hours heated to 130 ° C, the methyl alcohol formed being distilled off. The excess of the 3-cyclohexyl-3-oxo-propionic acid methyl ester is then distilled off in vacuo. An orange-yellow viscous oil of the very pure compound (19) is obtained in quantitative yield. This is used in the next reaction stage without further purification.

Level 2: N, N, N ', N'-tetrakis [6-cyclohexyl-5-diazo-4,6-dioxo-3-oxa-hexyl] ethylenediamine (20)

IR (KBr): 2.140,6 cm^-1 (C = N₂)19.8 9 (23 mmol) of the compound described above are dissolved in 200 ml of acetonitrile. 20.6 g (104 mmol) of tosyl azide are added to the solution, which is cooled to 0 ° C., and 10.8 g (107 mmol) of triethylamine are then added dropwise in such a way that the temperature does not rise above 50 ° C. After three hours, the clear, reddish solution is evaporated to dryness on a rotary evaporator, taken up in an ether / dichloromethane (3: 1) mixture, extracted twice with 100 ml of 5% aqueous potassium hydroxide solution and with 5% aqueous sodium chloride solution washed neutral. The organic phase is separated off and dried over magnesium sulfate. When concentrated on a rotary evaporator, the almost pure product (20) is already crystalline and in 95% yield. An analytically pure sample is prepared by recrystallization from ethanol; white crystals with a melting point of 112 - 114 ° C.

IR (KBr): 2,140.6 cm ^-1 (C = N ₂ )

Example 9 Preparation of a hexafunctional a-diazo-β-keto ester of the general formula I: 1,19-bis-cyclohexyl-2,18-bis-diazo-6,14- [bis- (4-cyclohexyl-3-diazo-2,4 -dioxo-1-oxa) butyl] -10- [8- (cyclohexyl-7-diazo-1,5-dioxa-6,8-dioxo-3- (3-cyclohexyl-3-diazo-2,4- dioxo-1-oxabutyl)) - 1,5-dioxa-6,8-dioxo-octyl] -4,8,12,16-tetraoxa-1,3,17,19-tetraoxo-nonadecane (22) Step 1: 1,19-bis-cyclohexyl-6,14- [bis- (4-cyclohexyl-2,4-dioxo-1-oxa) butyl] -10- [8- (cyclohexyl-1,5-dioxa-6, 8-dioxo-3- (3-cyc! Ohexyl-2,4-dioxo-1-oxa-butyl)) - 1,5-dioxa-6.8-dioxo-octyl] -4,8,12,16-tetraoxa- 1,3,17,19-tetraoxononadecane (21)

6.32 g (20 mmol) of tetraglycerol are heated to 130 ° C. for 7.5 hours with 33.1 g (180 mmol) of ethyl 3-cyclohexyl-3-oxo-propionate, the methyl alcohol formed being distilled off. The excess of the 3-cyclohexyl-3-oxo-propionic acid methyl ester is then distilled off in vacuo. A virtually colorless glass-like product is obtained in quantitative yield from very pure 1,19-bis-cyclohexyl-6,14- [bis- (4-cyclohexyl-2,4-dioxo-1-oxa) butyl] -10- [ 8- (cyclohexyl-1,5-dioxa-6,8-dioxo-3- (3-cyclohexyl-2,4-dioxo-1-oxa-butyl)) - 1,5-dioxa-6,8-dioxo- octyl -] - 4,8,12,16-tetraoxa-1,3,17,19-tetraoxononadecane (21). This is used in the next reaction stage without further purification.

Level 2: 1,19-bis-cyclohexyl-2,18-bis-diazo-6,14- [bis- (3-diazo-4-cyclohexyl-2,4-dioxo-1-oxa-butyl] -10- [8- (cyclohexyl-7-diazo-1,5-dioxa-6,8-dioxo-3- (3-cyclohexyl-3-diazo-2,4-dioxo-1-oxa-butyl)) - 1,5-dioxa- 6,8-dioxo-octyl] -4,8,12,16-tetraoxa-1,3,17,19-tetraoxo-nonadecane (22)

IR (Film): 2.138,4 cm-' (C=N₂)12.3 g (10 mmol) of compound (21) are dissolved in 150 ml of acetonitrile and, as described above, 11.8 g (60 mmol) of tosyl azide and 6.1 g (60 mmol) of triethylamine are added. After warming to room temperature, the mixture is stirred for 8 hours and worked up as described above. Half of the product mixture is eluted on a silica gel column, a light yellow fraction being isolated using the mobile phase dichloromethane / ethyl acetate (6: 1). After concentration, a yellowish oil remains.

IR (film): 2,138.4 cm- '(C = N ₂ )

Example 10

As described in Example 7, 10 g (73.5 mmol) of pentaerythritol are reacted with 55.2 g of 3-cyclohexyl-3-oxo-propionate and worked up. A tetrafunctional ester (compound 23) in which R ¹ = C ₆ H ₁₁ can be isolated. It is obtained as a viscous oil in almost quantitative yield.

Beispiel 11 (Vergleichsbeispiel)The ester (23) is then reacted with 59.1 g (300 mmol) of toluenesulfonyl azide and 30.6 g (300 mmol) of triethylamine in 200.0 g of acetonitrile to give the corresponding tetrafunctional a-diazo-β-keto ester of the general formula I. The compound (25) is purified by recrystallization from ethanol. It shows a melting point of 123 - 125 "C.

Example 11 (comparative example)

As described in Example 10, 10 g of pentaerythritol are converted to a tetrafunctional ester (compound 24), but in this case with 39.0 g of methyl acetoacetate, so that R '= CH ₃ .

Then the compound (24), as described in Example 10, is converted to the corresponding tetrafunctional a-diazo-β-keto ester (26) of the general formula I, and the compound (26) is recrystallized from ethanol. It shows a melting point of 108-120 ^* C.

As shown in the simultaneously filed German Patent Application P (Hoe 89 / K 002), point light-sensitive mixtures which contain the compound according to Example 11 as a photoactive component, in comparison to the compound of the invention of general formula I although comparable Ausbleic _h properties with these, however, the image differentiating properties are not satisfactory.

Examples 12 to 67

There are presented further compounds of general formula I, which were prepared analogously to the examples described so far. Because of the large number of compounds, these are characterized in the following tables with regard to the possible variations described in the general formula I. The quantitative determination of nitrogen is sufficiently meaningful as an analytical value.

C ₄ H ₇ - = cyclobutyl-; C ₆ H ₁₁ - = cyclohexyl.

Examples of use

The following examples show some possible uses of the radiation-sensitive mixtures according to the invention. These are intended to be illustrative only, but not to limit the invention. In the examples, parts by weight (pbw) to parts by volume (pbv) or g: cm ³ are 1: 1.

example 1

• 0,19 Gt 2,2,2-Tris-[4-(7-cyclohexyl-6-diazo-1,4-dioxa-7,5-dioxo-heptyl)-phenyl]-ethan (Beispiel 6) und
• 0,75 Gt Poly-(3-methyl-4-hydroxystyrol) in
• 4,25 Gt Propylenglykolmonomethyletheracetat.

A radiation sensitive mixture is prepared containing

• 0.19 pbw of 2,2,2-tris [4- (7-cyclohexyl-6-diazo-1,4-dioxa-7,5-dioxo-heptyl) phenyl] ethane (Example 6) and
• 0.75 pbw of poly (3-methyl-4-hydroxystyrene) in
• 4.25 pbw of propylene glycol monomethyl ether acetate.

1.5 ml of this solution are filtered through a filter with a pore diameter of 0.2 μm and applied to a silicon wafer with a diameter of 7.62 cm. By rotating the wafer at 2,000 rpm for 40 seconds, a homogeneous layer is produced which, after drying in a forced air oven at 90 ° C. and for 30 minutes, has a thickness of 0.87 μm.

The wafer coated in this way is imagewise irradiated through a photomask with the UV radiation of a xenon mercury vapor lamp at 260 nm with an energy of 112 mJ / cm ³ .

The imagewise irradiated layer is then developed with a 0.3 N aqueous solution of tetramethylammonium hydroxide for 120 sec. The removal of the layer in the unexposed areas (dark removal) was less than 20 nm. Structures, even with dimensions of less than 1.0 µm, were resolved with good edge stability.

Example 2

• 0,19 Gt N-Cylohexyl-N'-tris-[(5-cyclohexyl-4-diazo-3,5-dioxo-2-oxa)-pentyl]-methyl-harnstoff (Beispiel 45) und
• 0,75 Gt Poly-(3-methyl-4-hydroxystyrol) in
• 4,25 Gt Propylenglykolmonomethyletheracetat.

A radiation sensitive mixture is prepared containing

• 0.19 pbw of N-cyclohexyl-N'-tris - [(5-cyclohexyl-4-diazo-3,5-dioxo-2-oxa) pentyl] methyl urea (Example 45) and
• 0.75 pbw of poly (3-methyl-4-hydroxystyrene) in
• 4.25 pbw of propylene glycol monomethyl ether acetate.

A radiation-sensitive mixture is prepared from this solution using the information from Example 1. Exposure and development are carried out analogously to Example 1. However, an exposure energy of 60 mJ / cm ^{2 is} used for the exposure. Sharp-edged structures could be obtained.

Example 3

• 0,19 Gt Tris-[(5-diazo-4,6-dioxo-3-oxa-7-phenyl)-heptyl]-amin (Beispiel 40) und
• 0,75 Gt Poly-(3-methyl-4-hydroxystyrol) in
• 4,25 Gt Propylenglykolmonomethyletheracetat,
• und entsprechend dem Beispiel 2 weiterverarbeitet. Bei einer bildmäßigen Bestrahlung mit einer Energie von 71 mJ/cm² konnten kantenscharfe Strukturen erhalten werden.

A radiation sensitive mixture is prepared containing

• 0.19 pbw of Tris - [(5-diazo-4,6-dioxo-3-oxa-7-phenyl) heptyl] amine (Example 40) and
• 0.75 pbw of poly (3-methyl-4-hydroxystyrene) in
• 4.25 pbw of propylene glycol monomethyl ether acetate,
• and processed according to Example 2. With image-wise irradiation with an energy of 71 mJ / cm ² , sharp-edged structures could be obtained.

Example 4

• 0,19 Gt Tris-[(5-diazo-4,6-dioxo-3-oxa-7-phenyl)-heptyl]-amin und
• 0,55 Gt Poly-(styrol-co-maleinimid) (1:1) in
• 4,45 Gt Cyclohexanon.

A radiation sensitive mixture is prepared containing

• 0.19 pbw of tris - [(5-diazo-4,6-dioxo-3-oxa-7-phenyl) heptyl] amine and
• 0.55 pbw of poly (styrene-co-maleimide) (1: 1) in
• 4.45 pbw of cyclohexanone.

1.5 ml of this solution are filtered using a filter with a pore diameter of 0.2 μm and applied to a silicon wafer rotating at 2,000 rpm with a diameter of 7.62 cm. A homogeneous layer can be obtained after 40 sec. After drying the layer at 90 ° C. and for 30 minutes, the layer thickness of the homogeneous radiation-sensitive layer is 0.891 μm.

At a wavelength of 260 nm, the coated wafer is then exposed imagewise through a photomask. A xenon mercury vapor lamp is used as the UV radiation source. The exposure energy is 200 mJ / cm ^2.

With a 0.02N aqueous solution of tetramethylammonium hydroxide, the layer could then be developed perfectly within 60 seconds. The dark erosion was less than 10 nm; Structures 1.0 µm wide showed good resolution with good edge steepness.

Examples 5 to 14

Analogously to Example 4, but using the photoactive compounds listed below, radiation-sensitive mixtures were prepared and processed. In all cases, high resolution was achieved using the specified exposure energy.

Example 15

• 0,19 Gt der Verbindung (25) aus dem Herstellungsbeispiel 10 und
• 0,55 Gt Poly-(styrol-co-maleinimid) (1:1) in
• 4,45 Gt Cyclohexanon.

A radiation sensitive mixture is prepared containing

• 0.19 pbw of compound (25) from Preparation 10 and
• 0.55 pbw of poly (styrene-co-maleimide) (1: 1) in
• 4.45 pbw of cyclohexanone.

1.5 ml of the solution are spun through a filter with a pore diameter of 0.2 μm onto a silicon wafer with a diameter of 7.62 cm and a homogeneous layer is produced within 40 seconds by rotating the wafer at 4,000 rpm. The layer thickness after drying at 90 ^. C for 30 minutes in a forced air oven is 0.87 µm.

The coated wafer is irradiated through a photomask with UV radiation from a xenon mercury vapor lamp in the range of 260 nm with an exposure energy of 200 mJ / cm ² . Then ßend is developed with a 0.3 N aqueous solution of tetraethylammonium hydroxide within 60 seconds. The dark removal was less than 2 nm / min. When using an exposure energy of 116 mJ / cm ² , 1 µm structures could be resolved cleanly and with sharp edges.

Example 16 (comparative example)

• 0,19 Gt der Verbindung (26) aus dem Vergleichsbeispiel 11 und
• 0,55 Gt Poly-(styrol-co-maleinimid) (1:1) in
• 4,45 Gt Cyclohexanon.

A radiation sensitive mixture is prepared containing

• 0.19 pbw of compound (26) from Comparative Example 11 and
• 0.55 pbw of poly (styrene-co-maleimide) (1: 1) in
• 4.45 pbw of cyclohexanone.

The mixture is processed analogously to Example 15. However, it was found that after a development time of 60 seconds with the same developer from Example 15, both the exposed and unexposed areas had been completely removed. The removal of the unexposed areas (dark removal) at 1,660 nm / min was comparable to the removal rate for the exposed areas (2,360 nm / min). Structures could only be created using the development time of 20 seconds, but with very flat edges.

Claims (32)

1. A positive-working radiation-sensitive mixture, comprising essentially a photoactive component and a water-insoluble, at least swellable binder which is soluble in aqueous alkaline solution, characterized in that a polyfunctional a-diazo-β-keto ester of the general formula I is used as the photoactive component is used

wherein R 'is an aliphatic, cycloaliphatic or araliphatic or aromatic radical having 4 to 20 carbon atoms, it being possible for individual CH ₂ groups to be replaced by oxygen or sulfur atoms or by N or NH groups and / or to contain keto groups, X is an aliphatic, cycloaliphatic, carbocyclic, heterocyclic or araliphatic radical having 2 to 22 carbon atoms, individual CH _z groups being represented by oxygen or sulfur atoms or by the groups -NR ^2- , -C (O) -O-, -C ( 0) -NR ^2- , -C (O) -N -, -NR ^2- C (0) -NR ^3- , -OC (0) -NR ^2- , -OC (O) - N -, -OC (O) -O- or CH groups can be replaced by - N -, in which R ² and R ³ independently of one another represent hydrogen or an aliphatic, carbocyclic or araliphatic radical, m is an integer from 2 to 10 and n is an integer from 0 to 2 mean with the proviso that mn ≧ 2. 2. Positive-working radiation-sensitive mixture according to claim 1, characterized in that R ₂ and R _{3 are} hydrogen, (C ₁ -C ₃ ) alkyl, (C ₆ -C ₁₂ ) aryl or (C ₆ -C ₁₁ ) aralkyl, in particular ( C, -C ₃ ) are alkyl or hydrogen, where these, in particular aryl or aralkyl, can be substituted at the core by alkyl, alkoxy, halogen or amino. 3. positive-working radiation-sensitive mixture according to claims 1 or 2, characterized in that R 'and / or X are substituted by (C ₁ -C ₃ ) alkyl, (C ₁ -C ₃ ) alkoxy, halogen, amino or nitrilo, in particular by (C, -C ₃ ) alkyl or (C ₁ -C ₃ ) alkoxy. 4. positive working radiation-sensitive mixture according to one or more of claims 1 to 3, characterized in that if R 'is an aliphatic radical and this is substituted, this in particular has 4 to 8, chain links. 5. positive working radiation-sensitive mixture according to claim 4, characterized in that CH ₂ groups are replaced in particular by oxygen atoms, -NH groups or keto groups and these Residues therefore contain ether, keto, ester, amido and / or imido groups. 6. A positive-working radiation-sensitive mixture according to one or more of claims 1 to 3, characterized in that if R 'represents an aliphatic radical and this is unsubstituted, this can have up to 20 chain links, the t-butyl radical being particularly preferred. 7. positive working radiation-sensitive mixture according to one or more of claims 1 to 3, characterized in that R 'is a cycloaliphatic radical having 4, 5, 6 or 12, in particular 4, 5 or 6, particularly preferably 6, ring members, and the is particularly unsubstituted. 8. A positive-working radiation-sensitive mixture according to one or more of claims 1 to 3, characterized in that R 'is an araliphatic radical with 2 to 11, in particular 2 to 5, chain links in the aliphatic part of the rest. 9. positive working radiation-sensitive mixture according to claim 8, characterized in that the aliphatic part of the radical R 'contains 1 or 2 chain links, provided that this part has a pure carbon chain. 10. A positive-working radiation-sensitive mixture according to claim 8, characterized in that the aliphatic part of the radical R 'has 3 to 5 chain links, provided that CH ₂ groups are replaced by heteroatoms in this part. 11. positive-working radiation-sensitive mixture according to one or more of claims 1 to 10, characterized in that in the radical X a maximum of 5, in particular a maximum of 3 CH _z groups are replaced by the heteroatoms or the groups mentioned. 12. A positive-working radiation-sensitive mixture according to one or more of claims 1 to 10, characterized in that the radical X is aliphatic and unsubstituted and has a maximum of 6 carbon atoms. 13. A positive-working radiation-sensitive mixture according to claim 12, characterized in that it has a maximum of one C-C multiple bond. 14. A positive-working radiation-sensitive mixture as claimed in claim 11, characterized in that the heteroatoms which replace CH ₂ groups are of one type. 15. A positive-working radiation-sensitive mixture according to claim 11, characterized in that if a CH group is replaced by - N -, there is no further substitution in the radical X. 16. A positive-working radiation-sensitive mixture according to claim 11, characterized in that X is a cycloaliphatic radical in which the cycloaliphatic part is unsubstituted and is adjacent to a CH ₂ group of the aliphatic part which is substituted by a hetero atom or a group of the claim 1. 17. A positive-working radiation-sensitive mixture according to claim 16, characterized in that the cycloaliphatic part is directly adjacent to a nitrogen atom, in particular the groups

or

18. Positive working radiation-sensitive mixture according to claim 16, characterized in that the cycloaliphatic part via an ethylene group with the oxygen atom

Rest is linked. 19. A positive-working radiation-sensitive mixture according to claim 11, characterized in that X is an araliphatic radical, the aromatic part being in particular a phenyl or phenylene radical which is linked via a hetero atom to the aliphatic part of this radical. 20. A positive-working radiation-sensitive mixture according to one or more of claims 1 to 19, characterized in that m is an integer from 2 to 8 and n is an integer from 0 to 2. 21. A positive-working radiation-sensitive mixture according to claim 20, characterized in that m is an integer from 2 to 6 and n = 0. 22. A positive-working radiation-sensitive mixture according to one or more of claims 1 to 21, characterized in that a mixture of several, in particular 2 a-diazo-β-keto esters of the general formula I are contained in the radiation-sensitive mixture. 23. A positive-working radiation-sensitive mixture according to one or more of claims 1 to 22, characterized in that the concentration of the photoactive components in the radiation-sensitive mixture is 4 to 40% by weight, in particular 6 to 30% by weight. 24. A positive-working radiation-sensitive mixture according to one or more of claims 1 to 23, characterized in that the binder has a low self-absorption in the wavelength range from 190 to 300 nm. 25. A positive-working radiation-sensitive mixture according to one or more of claims 1 to 24, characterized in that the binder contains up to 30% by weight, in particular up to 20% by weight, of a novolak condensation resin. 26. A positive-working radiation-sensitive mixture according to one or more of claims 1 to 25, characterized in that the binder contains phenolic hydroxyl groups. 27. A positive-working radiation-sensitive mixture as claimed in one or more of claims 1 to 26, characterized in that the binder is present in the radiation-sensitive mixture in a concentration of 60 to 96% by weight, in particular 70 to 94% by weight. 28. A positive working recording material containing a carrier and a positive working mixture applied thereon, characterized in that the positive working mixture corresponds to a mixture according to one or more of claims 1 to 27. 29. A method for producing a positive-working recording material according to claim 28, characterized in that the carrier, which may have been pretreated with an adhesion promoter, is coated with the radiation-sensitive mixture by spraying, rolling, knife coating, pouring, by flow coating, spin coating and dip coating or by means of slot dies the solvent is removed by evaporation, so that a layer thickness of 0.1 to 100 µm, in particular 0.3 to 10 µm, arises. 30. The method according to claim 29, characterized in that the recording material is imagewise exposed to light with a wavelength of 190 to 300 nm and the resulting image is exposed by means of an aqueous developing solution. 31. The method according to claims 29 or 30, characterized in that the resulting structure is post-cured by heating and / or by exposure over the entire surface. 32. The method according to claim 29, characterized in that the radiation-sensitive mixture is applied to an intermediate carrier, and from which is only laminated onto the final carrier.